DE102004036583A1 - Plug components, with improved mechanical properties are prepared by injection molding of a thermoplastic polyester, a nucleating agent and a lubricant - Google Patents

Abstract

Plug components (I) are prepared by injection molding of a polyester molding composition (II) comprising: (a) 10-89.98 wt.% of a thermoplastic polyester; (b) 0.01-5 wt.% of a nucleating agent; and (c) 0.01-5 wt.% of a lubricant and; 0-30 wt.% of other additives.

Description

• A) 10 bis 89,98 Gew.-% eines thermoplastischen Polyesters
• B) 0,01 bis 5 Gew.-% mindestens eines Nukleierungsmittels
• C) 0,01 bis 5 Gew.-% mindestens eines Schmiermittels
• D) 0 bis 30 Gew.-% weiterer Zusatzstoffe, wobei die Summe der Gewichtsprozente der Komponenten A) bis D) 100 % ergibt.

The invention relates to plugs, plug parts, film hinges, these molded articles being obtainable from polyester molding compositions by injection molding, characterized in that the polyester molding compositions essentially comprise:

• A) 10 to 89.98 wt .-% of a thermoplastic polyester
• B) 0.01 to 5 wt .-% of at least one nucleating agent
• C) 0.01 to 5 wt .-% of at least one lubricant
• D) 0 to 30 wt .-% of other additives, wherein the sum of the weight percent of components A) to D) gives 100%.

Farther The invention relates to the use of such moldings for the production of components in the so-called E / E area (electronics and electrical area).

Unreinforced polyester are often used in the E / E field to make connectors with snap connections or film hinges used. The material is especially suitable due to the added demolding aid for processing by injection molding.

at the production or further processing of the components becomes special at unreinforced Material observed an uncontrolled fracture behavior.

The Some parts already fail when falling out from the injection mold, at a later Plugging or impact during the Assembly (for example, when "whipping" mounted plugs in wiring harnesses, which are unpacked at the car manufacturer).

Around To improve the fracture behavior has been tried, the impact resistance to optimize the material. To this end, different impact modifiers - e.g. on Elastomer base - in Polyester incorporated. The result was usually always an increase the impact resistance combined with an increase in Melt viscosity. The raised Working viscosity leads however Injection molded parts in the E / E area often cause problems. The fine ones and thin-walled Component structures and shapes can with the filled Material no longer complete filled become.

It There is thus a requirement in practice for a material with improved fracture behavior with constant flowability.

The Fracture behavior of semi-crystalline thermoplastics is due to the shape and shape of the spherulites of the semi-crystalline polyester. A crack propagation usually takes place along the spherulite boundaries. In addition, can the crack initiation is favored by larger spherulites.

task The present invention was therefore, plugs, connector parts and To provide film hinges made of polyesters, which a improved fracture behavior with constant processability (flowability) and while preserving the mechanical properties as much as possible exhibit.

Accordingly, were the initially defined moldings found. Preferred embodiments are the dependent claims refer to.

When Component (A) contain the polyester molding compositions 10 to 89.98, preferably 20 to 85 and in particular 30 to 80 wt .-% of a thermoplastic Polyester, preferably having a viscosity number of at least 85 ml / g, preferably at least 150 ml / g.

Generally are polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound used.

A first group of preferred polyesters are polyalkylene terephthalates, especially those having 2 to 10 carbon atoms in the alcohol part.

such Polyalkylene terephthalates are known per se and in the literature described. They contain an aromatic ring in the main chain, derived from the aromatic dicarboxylic acid. The aromatic Ring may also be substituted, e.g. by halogen like chlorine and Bromine or by C1-C4-alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.

These Polyalkylene terephthalates can by reaction of aromatic dicarboxylic acids, their esters or others ester-forming derivatives with aliphatic dihydroxy compounds be prepared in a conventional manner.

When preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or to name their mixtures. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic, azelaic, sebacic, dodecanedioic and cyclohexanedicarboxylic be replaced.

From the aliphatic dihydroxy compounds are diols having 2 to 6 Carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof are preferred.

When particularly preferred polyesters (A) are polyalkylene terephthalates, which are derived from alkanediols having 2 to 6 carbon atoms, to name. Of these, in particular, polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof. Farther preferred are PET and / or PBT, which up to 1 wt .-%, preferably up to 0.75% by weight of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further Contain monomer units.

The viscosity the polyester (A) is generally in a 0.5 wt .-% solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C) according to ISO 1628 measured.

Prefers are polyesters whose carboxyl end group content is greater than 15 mmol / kg, particularly preferably greater than 18 mmol / kg. such Polyester can For example, according to the method of DE-A 44 01 055 produced become. The carboxyl end group content is usually by titration (e.g., potentiometry).

Farther Is it advantageous to recycle PET (also called scrap-PET) if necessary in mixture with polyalkylene terephthalates such as PBT.

• 1) sog. Post Industrial Rezyklat: hierbei handelt es sich um Produktionsabfälle bei der Polykondensation oder bei der Verarbeitung z.B. Angüsse bei der Spritzgußverarbeitung, Anfahrware bei der Spritzgußverarbeitung oder Extrusion oder Randabschnitte von extrudierten Platten oder Folien.
• 2) Post Consumer Rezyklat: hierbei handelt es sich um Kunststoffartikel, die nach der Nutzung durch den Endverbraucher gesammelt und aufbereitet werden. Der mengenmäßig bei weitem dominierende Artikel sind blasgeformte PET Flaschen für Mineralwasser, Softdrinks und Säfte.

Recyclates are generally understood as:

• 1) so-called Post Industrial Recyclate: this is production waste in the polycondensation or during processing, for example, sprues in the injection molding, Anfahrware in the injection molding or extrusion or edge portions of extruded sheets or films.
• 2) Post Consumer Recyclate: These are plastic items that are collected and processed after use by the end user. By far the dominating items in terms of volume are blow-molded PET bottles for mineral water, soft drinks and juices.

Both Types of recyclate can either as regrind or in the form of granules. In the latter Case become the tube cyclates after separation and cleaning melted in an extruder and granulated. This will usually the handling, the flowability and the dosability for facilitates further processing steps.

Either Granulated as well as regrind present recyclates can for Use come, the maximum edge length 6 mm, preferably smaller Should be 5 mm.

by virtue of the hydrolytic cleavage of polyesters during processing (by traces of moisture) it is advisable to pre-dry the recyclate. The residual moisture content after drying is preferably <0.2%, in particular <0.05%.

When Another group are fully aromatic polyesters to name each other of aromatic dicarboxylic acids and aromatic dihydroxy compounds.

Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to mixtures of from 5 to 100 mol% of isophthalic acid and from 0 to 95 mol% Terephthalic acid, especially mixtures of about 80% terephthalic acid with 20% isophthalic acid to about equivalent mixtures of these two acids used.

in der Z eine Alkylen- oder Cycloalkylengruppe mit bis zu 8 C-Atomen, eine Anlengruppe mit bis zu 12 C-Atomen, eine Carbonylgruppe, eine Sulfonylgruppe, ein Sauerstoff- oder Schwefelatom oder eine chemische Bindung darstellt und in der m den Wert 0 bis 2 hat. Die Verbindungen können an den Phenylengruppen auch C₁-C₆-Alkyl- oder Alkoxygruppen und Fluor, Chlor oder Brom als Substituenten tragen.The aromatic dihydroxy compounds preferably have the general formula

in which Z is an alkylene or cycloalkylene group having up to 8 carbon atoms, an olefin group having up to 12 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m is 0 to 2 has. The compounds may also carry C ₁ -C ₆ -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.

As a parent of these compounds his example
dihydroxydiphenyl,
Di (hydroxyphenyl) alkane,
Di (hydroxyphenyl) cycloalkane,
Di (hydroxyphenyl) sulfide,
Di (hydroxyphenyl) ether,
Di (hydroxyphenyl) ketone,
di- (hydroxyphenyl) sulfoxide,
a, a'-di- (hydroxyphenyl) -dialkylbenzol,
Di (hydroxyphenyl) sulfone, di (hydroxybenzoyl) benzene
Resorcinol and
Hydroquinone and their nuclear alkylated or kemhalogenierte derivatives called.

Of these will be
4,4'-dihydroxydiphenyl,
2,4-di- (4'-hydroxyphenyl) -2-methylbutane
a, a'-di- (4-hydroxyphenyl) -p-diisopropylbenzene,
2,2-di- (3'-methyl-4'-hydroxyphenyl) propane and
2,2-di- (3'-chloro-4'-hydroxyphenyl) propane,
and in particular
2,2-di- (4'-hydroxyphenyl) propane
2,2-di- (3 ', 5-dichlordihydroxyphenyl) propane,
1,1-di- (4'-hydroxyphenyl) cyclohexane,
3,4'-dihydroxybenzophenone,
4,4'-dihydroxydiphenylsulfone and
2,2-di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane
or mixtures thereof are preferred.

Of course you can also mixtures of polyalkylene terephthalates and wholly aromatic polyesters deploy. These generally contain from 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of the wholly aromatic polyester.

Of course, polyester block copolymers such as copolyetheresters may also be used. Such products are known per se and described in the literature, for example in US Pat. No. 3,651,014. Also in the trade corresponding products are available, eg Hytrel ^® (DuPont).

Prefers The component A) has a Sphärolithgröße of smaller 15 microns, in particular less than 10 μm on.

These becomes common determined by scanning electron microscopy or light microscopy; the spherulites or Kristalllite become common by etching processes made visible.

Especially the component A) has a crystallization exotherm of greater than 40 J / g preferably greater than 45 J / g on.

In general, this parameter is determined by calorimetric method, such. B. DSC (Differen tial Scanning Calorimetry).

When Component B) contain the polyester molding compositions 0.01 to 5 wt .-%, preferably 0.02 to 1 wt .-% and in particular 0.02 to 0.05 wt .-% a nucleating agent.

When Nucleating agents are all known compounds in question For example, boron compounds such as boron nitride, silica, pigments such as. Heliogen blue (copper phthalocyanine pigment, registered trademark BASF Aktiengesellschaft), Russian, magnesium sulfate, mica, magnesium oxide, Titanium dioxide rutile and anatase modification.

In particular, as a nucleating agent talc is used, which is a hydrated magnesium silicate of the composition Mg ₃ [(OH) ₂ / Si ₄ O ₁₀ ] or 3 MgO · 4 SiO ₂ H ₂ O. These so-called three-layer phyllosilicates have a triclinic, monoclinic or rhombic crystal structure with a platelet-like appearance. On further trace elements Mn, Ti, Cr, Ni, Na and K may be present, wherein the OH group may be partially replaced by fluoride.

Particular preference is given to using talc whose particle sizes are 100% <20 μm. The particle size distribution is usually determined by sedimentation analysis and is preferably:
<20 μm 100% by weight
<10 μm 99% by weight
<5 μm 85% by weight
<3 μm 60% by weight
<2 μm 43% by weight

such Products are commercially available as Micro-Talc I.T. extra (Norwegian company Talc Minerals).

When Component C) contain the polyester molding compositions 0.01 to 5, preferably 0.05 to 1 and in particular 0.1 to 0.5 wt .-% of at least one Lubricant. Preferred lubricants are esters or amides more saturated or unsaturated aliphatic carboxylic acids with 10 to 40, preferably 16 to 22 carbon atoms with aliphatic saturated Alcohols or amines having 2 to 40, preferably 2 to 6 carbon atoms contain.

The carboxylic acids can Be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid as well as montanic acid (Mixture of fatty acids with 30 to 40 carbon atoms).

The Aliphatic alcohols can Be 1- to 4-valued. Examples of alcohols are n-butanol, n-octanol, Stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, Pentaerythritol, with ethylene glycol, glycerol and pentaerythritol preferred are.

The aliphatic amines can Be 1- to 3-valued. Examples of these are stearylamine, ethylenediamine, Propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, wherein Ethylenediamine and hexamethylenediamine are particularly preferred. preferred Esters or amides are according to glycerol distearate, glycerol tristearate, Ethylene diamine distearate, glycerol monopalmitate, glycerol trilaurate, Glycerol monobehenate and pentaerythritol tetrastearate.

It can also mixtures of different esters or amides or esters with amides be used in combination, the mixing ratio arbitrary is.

The molding compositions according to the invention can up to 30, preferably up to 25 and in particular up to 20 wt .-% further additives D).

Further Additives D) are, for example, in amounts of up to 30, preferably Up to 20 wt .-% of elastomeric polymers (often as impact modifiers, Elastomers or rubbers).

All in general, these are copolymers which are preferred are made up of at least two of the following monomers: ethylene, Propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, Acrylonitrile and acrylic or methacrylic acid esters having 1 to 18 carbon atoms in the alcohol component.

Such polymers are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Ge org-Thieme-Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph by CB Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977).

in the Following are some preferred types of such elastomers.

preferred Types of such elastomers are the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally have virtually no double bonds while EPDM rubbers 1 to 20 double bonds / 100 carbon atoms may have.

When Diene monomers for EPDM rubbers are, for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes of 5 to 25 C atoms such as Penta-1,4-diene, Hexa-1,4-diene, hexa-1,5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof. Preference is given to hexa-1,5-diene, 5-ethylidenenorbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.

EPM or EPDM rubbers can preferably also grafted with reactive carboxylic acids or their derivatives be. Here are e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as maleic anhydride called.

wobei R¹ bis R⁹ Wasserstoff oder Alkylgruppen mit 1 bis 6 C-Atomen darstellen und m eine ganze Zahl von 0 bis 20, g eine ganze Zahl von 0 bis 10 und p eine ganze Zahl von 0 bis 5 ist.Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids. In addition, the rubbers may also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, for example esters and anhydrides, and / or monomers containing epoxy groups. These dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by addition of monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture R ¹ COOR ² ) = C (COO R ³ ) R ⁴ (I)

wherein R ¹ to R ^{9 represent} hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer of 0 to 20, g is an integer of 0 to 10 and p is an integer of 0 to 5.

The radicals R ¹ to R ⁹ preferably denote hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

preferred Compounds of formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as Glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, come in Their behavior, however, is close to the free acids and therefore becomes referred to as monomers with latent carboxyl groups.

Advantageous The copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to 20 Wt .-% epoxy groups containing monomers and / or methacrylic acid and / or acid anhydride groups containing monomers and the remaining amount of (meth) acrylic acid esters.

Particularly preferred are copolymers of
50 to 98, in particular 55 to 95 wt .-% ethylene,
0.1 to 40, in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and
1 to 45, in particular 10 to 40 wt .-% n-butyl acrylate and / or 2-ethylhexyl acrylate.

Further preferred esters of acrylic and / or methacrylic acid are the methyl, ethyl, Propyl and i- or t-butyl ester.

Besides can Vinyl esters and vinyl ethers are also used as comonomers.

The The ethylene copolymers described above can be known per se Process are prepared, preferably by random copolymerization under high pressure and elevated Temperature. Corresponding methods are generally known.

preferred Elastomers are also emulsion polymers whose preparation is e.g. at Blackley in the monograph "Emulsion Polymerization "described becomes. The emulsifiers and catalysts that can be used are in themselves known.

Basically, can be homogeneous constructed elastomers or those used with a shell structure become. The shell-like construction is determined by the order of addition the individual monomers determined; also the morphology of the polymers is affected by this order of addition.

Just are representative here as monomers for the preparation of the rubber part the elastomers acrylates such as e.g. n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof called. These monomers can with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, Methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.

The Soft or rubber phase (with a glass transition temperature of below 0 ° C) the Elastomers may be the core, the outer shell or a middle shell (for elastomers with more than two-shell construction) group; in multi-shell elastomers can also be several shells a rubber phase.

are in addition to the rubber phase, one or more hard components (with glass transition temperatures of more than 20 ° C) involved in the construction of the elastomer, so these are in general by polymerization of styrene, acrylonitrile, methacrylonitrile, methylstyrene, p-methylstyrene, acrylic esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as major monomers produced.

Besides can Here, too, lower proportions of other comonomers are used.

eingeführt werden können,
wobei die Substituenten folgende Bedeutung haben können:
R¹⁰ Wasserstoff oder eine C₁- bis C₄-Alkylgruppe,
R¹¹ Wasserstoff, eine C₁- bis C₈-Alkylgruppe oder eine Arylgruppe, insbesondere Phenyl,
R¹² Wasserstoff, eine C₁- bis C₁₀-Alkyl-, eine C₆- bis C₁₂-Arylgruppe oder -OR¹³
R¹³ eine C₁- bis C₈-Alkyl- oder C₆- bis C₁₂-Arylgruppe, die gegebenenfalls mit O- oder N-haltigen Gruppen substituiert sein können,
X eine chemische Bindung, eine C₁- bis C₁₀-Alkylen- oder C₆-C₁₂-Arylengruppe oder

Y O-Z oder NH-Z und
Z eine C₁- bis C₁₀-Alkylen- oder C₆- bis C₁₂-Arylengruppe.In some cases it has proven to be advantageous to use emulsion polymers which have reactive groups on the surface. Such groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups obtained by concomitant use of monomers of the general formula

can be introduced
where the substituents may have the following meanings:
R ^{10 is} hydrogen or a C ₁ - to C ₄ -alkyl group,
R ^{11 is} hydrogen, a C ₁ - to C ₈ -alkyl group or an aryl group, in particular phenyl,
R ^{12 is} hydrogen, a C ₁ - to C ₁₀ -alkyl, a C ₆ - to C ₁₂ -aryl group or -OR ¹³
R ^{13 is} a C ₁ - to C ₈ -alkyl or C ₆ - to C ₁₂ -aryl group which may optionally be substituted by O- or N-containing groups,
X is a chemical bond, a C ₁ - to C ₁₀ -alkylene or C ₆ -C ₁₂ -arylene group or

Y OZ or NH-Z and
Z is a C ₁ - to C ₁₀ -alkylene or C ₆ - to C ₁₂ -arylene group.

Also in the EP-A 208 187 grafting monomers described are suitable for introducing reactive groups on the surface.

When other examples are acrylamide, methacrylamide and substituted Esters of acrylic acid or methacrylic acid such as (N-t-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) ethyl acrylate called.

Furthermore, the particles of the rubber phase can also be crosslinked. Examples of monomers acting as crosslinking agents are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate and those described in US Pat EP-A 50 265 described compounds.

Further can also so-called graft-linking monomers (graft-linking monomers) be used, i. Monomers with two or more polymerisable Double bonds, which in the polymerization with different Speeds respond. Preferably, such compounds used in which at least one reactive group with about the same Speed like the rest Monomers polymerized while the other reactive group (or reactive groups) e.g. clear polymerized more slowly (polymerize). The different ones Polymerization rates bring a certain proportion in unsaturated Double bonds in rubber with it. Will then open grafted such a rubber another phase, so react the double bonds present in the rubber at least partially with the grafting monomers forming chemical bonds, i.e. the grafted phase is at least partially chemical Bindings linked to the grafting base.

Examples of such graft-crosslinking monomers are allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids. In addition, there are a variety of other suitable graft-linking monomers; for more details, for example, on the U.S. Patent 4,148,846 directed.

in the general amounts the proportion of these crosslinking monomers in the impact-modifying polymer up to 5 wt .-%, preferably not more than 3 wt .-%, based on the impact resistant modifying polymers.

Instead of of graft polymers having a multi-shell construction can also homogeneous, i. single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or their copolymers are used. Also these products can by using crosslinking monomers or monomers with reactive Groups are produced.

Examples for preferred Emulsion polymers are n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having a inner core of n-butyl acrylate or butadiene-based and an outer shell of the above-mentioned copolymers and copolymers of ethylene with comonomers that provide reactive groups.

The described elastomers can also after other usual Method, e.g. by suspension polymerization.

Silicone rubbers, as in DE-A 37 25 576 , of the EP-A 235 690 , of the DE-A 38 00 603 and the EP-A 319 290 are also preferred.

Of course you can too Mixtures of the abovementioned Rubber types are used.

When fibrous or particulate fillers (Component D)) are carbon fibers, glass fibers, glass beads, amorphous silica, Asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, Chalk, powdered quartz, mica, barium sulphate and feldspar, in amounts up to 30 wt .-%, in particular 1 to 30%, and in particular 15 to 30 wt .-% are used.

When preferred fibrous fillers be called carbon fibers, aramid fibers and potassium titanate fibers, wherein glass fibers are particularly preferred as E glass. These can be as Rovings or chopped glass can be used in the commercial forms.

The fibrous fillers can for better compatibility surface pretreated with the thermoplastic with a silane compound be.

n eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4
m eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2
k eine ganze Zahl von 1 bis 3, bevorzugt 1Suitable silane compounds are those of the general formula (X- (CH ₂ ) _n ) _k -Si- (OC _m H _{2m + 1} ) _4-k in which the substituents have the following meanings:

n is an integer from 2 to 10, preferably 3 to 4
m is an integer from 1 to 5, preferably 1 to 2
k is an integer from 1 to 3, preferably 1

preferred Silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, Aminopropyltriethoxysilane, Aminobutyltriethoxysilane and the corresponding Silanes which contain a glycidyl group as substituent X.

The Silane compounds are generally used in amounts of from 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1 wt .-% (relative on D) for surface coating used.

Suitable are also acicular mineral fillers.

Under acicular mineral fillers becomes within the meaning of the invention a mineral filler with a pronounced needle-like character Understood. An example is acicular wollastonite. Preferably, the mineral has an L / D (length Diameter) ratio from 8: 1 to 35: 1, preferably from 8: 1 to 11: 1. The mineral filler optionally with the abovementioned silane compounds pretreated; however, the pretreatment is not necessarily required.

When further fillers are kaolin, calcined kaolin, wollastonite, talc and chalk called.

It can inorganic pigments, such as ultramarine blue, iron oxide, titanium dioxide, Zinc sulfide and carbon black, continue organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones as colorants be added and any flame retardants, which the expert common are.

When examples for Plasticizers are dioctyl phthalate, phthalate, phthalate, Hydrocarbon oils, Called N- (n-butyl) benzenesulfonamide.

The thermoplastic according to the invention Molding compounds can be prepared by methods known per se, in which the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and subsequently extruded. After extrusion, the extrudate can be cooled and be crushed. It can Also, individual components are premixed and then the remaining Starting materials are added individually and / or also mixed become.

To a preferred mode of operation the components B) to D) mixed with a polyester prepolymers A), formulated and granulated. The resulting granules are in solid phase subsequently under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity condensed. In usual Way, such molding compositions by injection molding to the plugs according to the invention, Plug parts and / or film hinges processed.

These show a good processability (flowability) and an improved Fracture behavior with largely constant mechanical properties.

Therefore Such shaped bodies are suitable for the production of components in the field of E / E such as wiring harness components, Circuit boards, Cable mount components, Three-dimensionally injection-molded circuit carriers, electrical connection elements, mechatronic components, optoelectronic components

• Component A: Polybutylene Terephthalate (PBT) Having a Viscosity Number (VZ) of 130 ml / g and a carboxyl end group content of 15 mol / kg (VZ measured in 0.5% by weight solution from phenol / o-dichlorobenzene, 1: 1 mixture at 25 ° C according to ISO 1628).
• Component B: Talc
• Component C: pentaeryl tetrastearate (Loxiol, P. 861 of Company Cognis GmbH)

Production of the molding compositions

The Components A) and C) were in the proportions shown in the table on an extruder at 260 ° C mixed, homogenized, granulated and dried. The component B was subsequently with the help of a mixer the granules drummed.

The following measurements were carried out:
The impact resistance was measured at 23 ° C according to ISO 179 / 1eU,
The impact strength was measured at 23 ° C according to ISO 179 / 1eA,
Elongation, breaking stress modulus and elongation at yield according to ISO 527.

The Results of the measurements are shown in the table.

Composition: Example 1V: 99.35% by weight A 0.65% by weight C
Example 1: 99.31% by weight A 0.65% by weight C
0.04 wt.% B

Table:

Claims (9)

Plugs, plug parts, plug connectors, film hinges, these moldings are obtainable from polyester molding compositions by injection molding, characterized in that the polyester molding compositions essentially comprise: A) 10 to 89.98 wt .-% of a thermoplastic polyester B) 0.01 to 5 wt .-% of at least one nucleating agent C) 0.01 to 5 wt .-% of at least one lubricant D) 0 to 30 wt .-% of further additives, wherein the sum of the weight percent of components A) to D) gives 100%. Plugs, plug parts, plug connectors, film hinges according to claim 1, characterized in that these snap connections exhibit. Plugs, plug parts, plug connectors, film hinges according to the claims 1 or 2, characterized in that the component A) has a viscosity number (VZ) of at least 85 ml / g. Plugs, plug parts, plug connectors, film hinges according to the claims 1 to 3, in which the component C) is composed of talc. Plugs, plug parts, plug connectors, film hinges according to the claims 1 to 4, in which the component A) is a Carboxylendgruppenzahl greater than 15 mmol / kg having. Plugs, plug parts, plug connectors, film hinges according to the claims 1 to 5, in which component A) is a polyalkylene terephthalate is. Plugs, plug parts, plug connectors, film hinges according to the claims 1 to 6, in which the component A) has a Sphärolithgröße of less than 15 microns. Plugs, plug parts, plug connectors, film hinges according to the claims 1 to 77, in which component A) a crystallization exotherm greater than 40 J / g having. Use of plug, plug parts, plug connector, Film hinges according to claims 1 to 8 for the production of components in the field of E / E such as wiring harness components, Circuit boards, Cable mount components, Three-dimensional injection-molded circuit carrier, electrical connection elements, mechatronic Components, optoelectronic components.